JP2016224129A - Yellow toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide yellow toners excellent in storage stability, such as a blocking property and environmental stability of chargeability and in light fastness.SOLUTION: A yellow toner comprises toner particles containing a colorant. The colorant contains a compound represented by one of the formulas (1) to (3).SELECTED DRAWING: None

Description

  The present invention relates to a yellow toner used in a recording method such as an electrophotographic method, an electrostatic recording method, a magnetic recording method, or a toner jet method.

  In recent years, there has been an increasing demand for higher image quality of color images. In color copiers and color printers, it is common to develop with each color toner of Y (yellow), M (magenta), C (cyan), and Bk (black) to form an image on a recording material. is there. Therefore, it is required to improve the performance of the colorant in each color toner.

  As colorants used in yellow toners, for example, compounds having an isoindolinone, quinophthalone, isoindoline, anthraquinone, anthrone, xanthene, or pyridone azo skeleton are known.

  Patent Document 1 discloses a toner containing a yellow colorant having a pyridone azo skeleton having excellent melt miscibility, image stability by repeated development, and good light fastness.

  Patent Documents 2 to 7 describe toners containing a yellow colorant having a pyridone azo skeleton with limited substituents and positions of substituents.

JP-A-1989-253759 WO95 / 34846 JP 2013-214058 A WO08 / 069045 JP-A-6-59510 Japanese Patent No. 2612294 JP 2011-257706 A

  The yellow toner described in the above-mentioned document has good color tone and coloring power, but needs to be further improved in terms of storage stability such as blocking property and charging environmental stability and light resistance.

  An object of the present invention is to provide a yellow toner which is excellent in storage stability such as blocking property and charging environmental stability and light resistance.

The present invention is a yellow toner having toner particles containing a binder resin and a colorant,
The colorant contains at least one compound selected from the group consisting of a compound represented by the following formula (1), a compound represented by the following formula (2), and a compound represented by the following formula (3). It relates to a characteristic yellow toner.

(In the formulas (1) to (3),
R ¹ , R ¹¹ , R ¹² and R ²¹ each independently represents an alkyl group having 3 or more carbon atoms.
R ³ , R ¹³ and R ²³ each independently represents an alkyl group.
R ⁴ , R ¹⁴ , and R ²⁴ each independently represent a linear alkyl group having 3 or more carbon atoms. )

  According to the present invention, it is possible to provide a yellow toner having excellent storage stability such as blocking property and charging environmental stability and light resistance.

  Hereinafter, the present invention will be described in more detail with reference to modes for carrying out the invention.

  The yellow toner of the present invention has toner particles containing a binder resin and a colorant. The colorant contains at least one compound selected from the group consisting of a compound represented by the following formula (1), a compound represented by the following formula (2), and a compound represented by the following formula (3). It is characterized by that.

In formulas (1) to (3), R ¹ , R ¹¹ , R ¹² and R ²¹ each independently represents an alkyl group having 3 or more carbon atoms. R ³ , R ¹³ and R ²³ each independently represents an alkyl group. R ⁴ , R ¹⁴ , and R ²⁴ each independently represent a linear alkyl group having 3 or more carbon atoms.

Examples of the alkyl group having 3 or more carbon atoms of R ¹ , R ¹¹ , R ¹² and R ²¹ include an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, n Saturated linear, branched, or cyclic primary to tertiary alkyl groups having 1 to 16 carbon atoms such as octyl group, cyclohexyl group, 2-ethylhexyl group and the like can be mentioned. R ¹ , R ¹¹ , R ¹² and R ²¹ are preferably an alkyl group having 3 to 8 carbon atoms.

Examples of the alkyl group for R ³ , R ^13, and R ²³ include a saturated linear or branched group such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a sec-butyl group, and an n-octyl group. And primary to tertiary alkyl groups having 1 to 16 carbon atoms. R ³ , R ¹³ and R ²³ are preferably an alkyl group having 1 to 8 carbon atoms.

Examples of the linear alkyl group having 3 or more carbon atoms of R ⁴ , R ¹⁴ , and R ²⁴ include an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, and an n-octyl group. And a saturated linear alkyl group having 1 to 16 carbon atoms. In R ⁴ , R ¹⁴ , and R ²⁴ , a linear alkyl group having 3 to 8 carbon atoms is preferable.

R ¹ , R ¹¹ , R ¹² and R ²¹ are preferably n-octyl group or 2-ethylhexyl group because of excellent light resistance.

  The compound represented by the formula (1) can be synthesized with reference to a known method described in JP2012-066729A.

  Specific examples of the compound represented by any one of formulas (1) to (3) are shown below, but are not particularly limited to the following compounds.

  The compounds represented by any one of the formulas (1) to (3) may be used alone or in combination with a known yellow dye in order to adjust the color tone or the like according to the toner production means. You can also.

  The compound represented by the formula (1) can also be combined with a yellow pigment. Examples of yellow pigments to be combined include C.I. I. Pigment Yellow 180, 155, 150, 74 and the like are preferable. These pigments may be used alone or in combination of two or more.

<Binder resin>
Examples of the binder resin include a thermoplastic resin.

  Specifically, homopolymers or copolymers of styrenes such as styrene, parachlorostyrene, α-methylstyrene (styrene resin); methyl acrylate, ethyl acrylate, n-propyl acrylate, n-acrylate -Homopolymers or copolymers of esters having vinyl groups such as butyl, lauryl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, etc. Polymer (vinyl resin); homopolymer or copolymer of vinyl nitriles such as acrylonitrile and methacrylonitrile (vinyl resin); vinyl ether homopolymer or copolymer such as vinyl ethyl ether and vinyl isobutyl ether ( Vinyl resin); vinyl methyl ketone, vinyl Homopolymers or copolymers of ethyl ketone and vinyl isopropenyl ketones (vinyl resins); Homopolymers or copolymers of olefins such as ethylene, propylene, butadiene, isoprene (olefin resins); epoxy resins, polyesters Examples thereof include non-vinyl condensation resins such as resins, polyurethane resins, polyamide resins, cellulose resins, and polyether resins, and graft polymers of these non-vinyl condensation resins and vinyl monomers. These resins may be used alone or in combination of two or more.

  The polyester resin is synthesized from an acid component (dicarboxylic acid) and an alcohol component (diol). The polyester resin has a constituent part derived from an acid component and a constituent part derived from an alcohol component.

  Examples of the acid component include aliphatic dicarboxylic acids, dicarboxylic acids having a double bond, and dicarboxylic acids having a sulfonic acid group. Specifically, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1, 11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, lower of them Examples include alkyl esters and acid anhydrides. In particular, an aliphatic dicarboxylic acid is desirable, and it is preferable that the aliphatic site in the aliphatic dicarboxylic acid is a saturated carboxylic acid.

  As the alcohol component, for example, an aliphatic diol is desirable. Specifically, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, , 9-nonanediol, 1,10-decanediol, 1,11-dodecanediol, 1,12-undecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, , 20-eicosanediol and the like.

  In the present invention, it is possible to use a crosslinking agent during the synthesis of the binder resin in order to increase the mechanical strength of the toner particles and to control the molecular weight of the toner molecules.

  As the crosslinking agent, for example, as difunctional crosslinking agent, divinylbenzene, bis (4-acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol di Acrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200, # 400, # 600 diacrylates, dipropylene glycol diacrylate, polypropylene glycol diacrylate, polyester-type diacrylate, and the above-described diacrylate The include those instead dimethacrylate.

  Examples of the multifunctional crosslinking agent include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate and its methacrylate, 2,2-bis (4-methacryloxy). Phenyl) propane, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate and triallyl trimellitate.

  These crosslinking agents are preferably used in an amount of 0.05 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the binder resin.

  Examples of the method for producing the toner particles constituting the toner of the present invention include a pulverization method, a suspension polymerization method, a suspension granulation method, an emulsion polymerization method, and an emulsion aggregation method. The pulverization method is a method of obtaining toner particles by kneading and pulverizing a resin composition containing a binder resin and a colorant. The suspension polymerization method is obtained by dispersing a polymerizable monomer composition containing a colorant and a polymerizable monomer in an aqueous medium to prepare a suspension, and then polymerizing the polymerizable monomer. In this method, toner particles containing the binder resin are obtained. The suspension granulation method is a method in which a solution containing a colorant and a binder resin is suspended in an aqueous solvent and granulated to obtain toner particles. The emulsion aggregation method is a method in which a dispersion liquid obtained by emulsifying and dispersing a binder resin and a dispersion liquid of a colorant are mixed, and aggregated and heat-fused to obtain toner particles.

  Among these, it is preferable to obtain toner particles by a production method in which granulation is performed in an aqueous medium such as suspension polymerization or suspension granulation. Further, it can also be used as a developer (hereinafter referred to as a liquid developer) used in the liquid development method.

<Dye dispersion>
The pigment dispersion of the present invention will be described. The dispersion medium refers to water, an organic solvent, or a mixture thereof.

  The dye dispersion of the present invention can be obtained by dispersing the dye compound represented by any one of the general formulas (1) to (3) in a dispersion medium. Specifically, the following method is mentioned, for example. In the dispersion medium, the dye compound represented by any one of the general formulas (1) to (3) and a resin are dissolved if necessary, and the mixture is sufficiently adapted to the dispersion medium while stirring. Furthermore, by applying mechanical shearing force with a dispersing machine such as a ball mill, paint shaker, dissolver, attritor, sand mill, or high speed mill, the dye compound can be stably finely dispersed into uniform fine particles.

  In this invention, it is preferable that the quantity of the pigment | dye compound in a pigment | dye dispersion is 1-30 mass parts with respect to 100 mass parts of dispersion media. More preferably, it is 2-20 mass parts, Most preferably, it is 3-15 mass parts. By setting the content of the dye compound within the above range, an increase in viscosity and a decrease in dispersibility of the dye compound can be suppressed, and good coloring power can be exhibited.

  The pigment dispersion can be dispersed in water using an emulsifier. Examples of the emulsifier include a cationic surfactant, an anionic surfactant, and a nonionic surfactant. Examples of the cationic surfactant include dodecyl ammonium chloride, dodecyl ammonium bromide, dodecyl trimethyl ammonium bromide, dodecyl pyridinium chloride, dodecyl pyridinium bromide, hexadecyl trimethyl ammonium bromide and the like. Examples of the anionic surfactant include fatty acid soaps such as sodium stearate and sodium dodecanoate, sodium dodecyl sulfate, sodium dodecylbenzene sulfate, and sodium lauryl sulfate. Nonionic surfactants include dodecyl polyoxyethylene ether, hexadecyl polyoxyethylene ether, nonylphenyl polyoxyethylene ether, lauryl polyoxyethylene ether, sorbitan monooleate polyoxyethylene ether, monodecanoyl sucrose, etc. It is done.

  Examples of the organic solvent used as the dispersion medium include the following. Methyl alcohol, ethyl alcohol, modified ethyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, sec-butyl alcohol, tert-amyl alcohol, 3-pentanol, octyl alcohol, benzyl alcohol, cyclohexanol, etc. Alcohols; methyl cellosolve, ethyl cellosolve, glycols such as diethylene glycol, diethylene glycol monobutyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; esters such as ethyl acetate, butyl acetate, ethyl propionate, cellosolve acetate; hexane , Octane, petroleum ether, cyclohexane, benzene, toluene, xylene and other hydrocarbon solvents; tetrachloride Halogenated hydrocarbon solvents such as silicon, trichloroethylene and tetrabromoethane; ethers such as diethyl ether, dimethyl glycol, trioxane and tetrahydrofuran; acetals such as methylal and diethyl acetal; organic acids such as formic acid, acetic acid and propionic acid; Sulfur / nitrogen-containing organic compounds such as nitrobenzene, dimethylamine, monoethanolamine, pyridine, dimethylsulfoxide, dimethylformamide.

  Moreover, it is preferable to use a polymerizable monomer for the pigment dispersion. The polymerizable monomer is an addition polymerizable or condensation polymerizable monomer, and is preferably an addition polymerizable monomer. Specifically, styrene monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene; methyl acrylate, ethyl acrylate Acrylates such as propyl acrylate, butyl acrylate, octyl acrylate, dodecyl acrylate, stearyl acrylate, behenyl acrylate, 2-ethylhexyl acrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, acrylonitrile, acrylamide Monomers: methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, octyl methacrylate, dodecyl methacrylate, stearyl methacrylate, behenyl methacrylate, 2-ethyl methacrylate Methyl monomers such as syl, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, methacrylonitrile, methacrylamide; olefin monomers such as ethylene, propylene, butylene, butadiene, isoprene, isobutylene, cyclohexene; Vinyl halides such as vinyl, vinylidene chloride, vinyl bromide and vinyl iodide; vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether And vinyl ketone compounds such as vinyl methyl ketone, vinyl hexyl ketone, and methyl isopropenyl ketone. These can be used alone or in combination of two or more according to the intended use. When the dye dispersion is used for a polymerized toner, it is preferable to use styrene or a styrene monomer alone or mixed with other polymerizable monomers among the polymerizable monomers. . Styrene is preferred because of its ease of handling.

  A resin may be further added to the pigment dispersion. The resin that can be used for the pigment dispersion is determined according to the intended use and is not particularly limited. Specifically, for example, polystyrene resin, styrene copolymer, polyacrylic acid resin, polymethacrylic acid resin, polyacrylic acid ester resin, polymethacrylic acid ester resin, acrylic acid copolymer, methacrylic acid copolymer , Polyester resin, polyvinyl ether resin, polyvinyl methyl ether resin, polyvinyl alcohol resin, polyvinyl butyral resin and the like. These resins can be used alone or in admixture of two or more.

  Moreover, it is preferable that content of the coloring agent containing a pigment dispersion is 1-20 mass parts with respect to 100 mass parts of binder resin. Within this range, a sufficient toner concentration is ensured and the colorant is sufficiently contained in the toner particles.

<Constituent materials of toner>
Next, constituent materials of the toner of the present invention will be described. The toner of the present invention is a toner including toner particles containing a binder resin and a colorant. When the toner is produced, the use of the pigment dispersion can suppress an increase in the dispersion viscosity in the dispersion medium, which facilitates handling in the toner production process and maintains good dispersibility of the colorant. Therefore, a yellow toner having a high coloring power can be provided.

  The toner particles of the present invention may contain a wax. Examples of the wax include petroleum waxes such as paraffin wax, microcrystalline wax, and petrolatum and derivatives thereof; montan wax and derivatives thereof; hydrocarbon waxes and derivatives thereof according to the Fischer-Tropsch method; polyolefin waxes such as polyethylene and polypropylene wax; Derivatives thereof: natural waxes such as carnauba wax and candelilla wax and their derivatives. These derivatives include oxides, block copolymers with vinyl monomers, and graft-modified products. Further examples include alcohols such as higher aliphatic alcohols, fatty acids such as stearic acid and palmitic acid, or compounds thereof, acid amide waxes, ester waxes, ketones, hydrogenated castor oil and derivatives thereof, plant waxes, and animal waxes. These waxes can be used alone or in combination of two or more.

  The wax is preferably contained in an amount of 2.5 to 15 parts by mass with respect to 100 parts by mass of the binder resin. More preferably, it is the range of 3-10 mass parts. The range of 2.5 to 15 parts by mass is preferable because oilless fixing becomes favorable and desired charging characteristics can be obtained without excessive presence of wax on the surface of the toner particles. Further, the content of the wax in the toner is preferably 1 to 25 parts by mass, more preferably 3 to 20 parts by mass with respect to 100 parts by mass of the toner particles. Within this range, it is possible to achieve both releasability and developability.

  The wax of the present invention preferably has a melting point of 50 ° C. or higher and 200 ° C. or lower, more preferably 55 ° C. or higher and 150 ° C. or lower. The melting point indicates a main endothermic peak temperature in a differential scanning calorimetry (DSC) curve measured according to ASTM D3418-82. Specifically, the melting point of the wax is measured using a differential scanning calorimeter (Metler Trade Co., Ltd .: DSC822), the measurement temperature range is 30 to 200 ° C., the heating rate is 5 ° C./min, and the temperature is normal temperature and humidity. A DSC curve in the temperature range of 30 to 200 ° C. is obtained by the second temperature raising process. The main endothermic peak temperature in the obtained DSC curve is the melting point of the wax.

  In the toner of the present invention, a charge control agent can be mixed with toner particles and used as necessary. As the charge control agent, known ones can be used, and examples of the toner that controls the toner negatively include the following. Polymers or copolymers having sulfonic acid groups, sulfonic acid groups or sulfonic acid ester groups, salicylic acid derivatives and their metal complexes, monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic mono- and polycarboxylic acids, Metal salts, anhydrides, esters, phenol derivatives such as bisphenol, urea derivatives, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, calixarene, and resin charge control agents.

  Examples of controlling the toner to be positively charged include the following. Modified products of nigrosine with nigrosine and fatty acid metal salts, quaternary ammonium salts such as guanidine compounds, imidazole compounds, tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and the like Onium salts such as phosphonium salts and these lake pigments, triphenylmethane dyes and these lake pigments Acid, ferricyanide, ferrocyanide, etc.), metal salts of higher fatty acids, diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide, dibutyltin , Dioctyl tin borate, diorgano tin borate such, resin charge control agent such as dicyclohexyl tin borate. In the toner of the present invention, these charge control agents can be used alone or in combination of two or more.

  In the toner of the present invention, an inorganic fine powder may be externally added as an external additive for improving fluidity. As the inorganic fine powder, fine powder such as silica, titanium oxide, alumina or a double oxide thereof, or a surface-treated product thereof can be used.

  The toner of the present invention has a weight average particle diameter (D4) of 4.0 to 9.0 μm, and a ratio of the weight average particle diameter to the number average particle diameter (D1) (hereinafter, D4 / D1) is 1.35 or less. It is preferable that Furthermore, it is more preferable that the weight average particle diameter D4 is 4.9 to 7.5 μm and D4 / D1 is 1.30 or less. When the weight average particle diameter is 4.0 μm or more, the charging stability is improved, and image deterioration such as image fogging and development streaks is suppressed in continuous development operation (endurance operation) of a large number of sheets. Further, when the weight average particle diameter is 8.0 μm or less, the reproducibility of the halftone portion is good. When D4 / D1 is 1.35 or less, fog and transferability are improved, and variations in thickness of line widths such as thin lines are reduced (hereinafter also referred to as sharpness).

  The toner of the present invention has an average circularity of 0.930 to 0.995, more preferably 0.960 to 0.990 as measured by a flow particle image analyzer. This is preferable because the transferability is greatly improved.

  Toner particles produced by the suspension polymerization method are produced, for example, as follows.

  First, a colorant containing a pigment dispersion, a polymerizable monomer, a wax and a polymerization initiator are mixed to prepare a polymerizable monomer composition. Next, the polymerizable monomer composition is dispersed in an aqueous medium containing a dispersion stabilizer prepared in advance to prepare a suspension (granulation step). Thereafter, the polymerizable monomer in the suspension is polymerized to obtain a binder resin. After the polymerizable monomer is polymerized to obtain a binder resin, a solvent removal treatment is performed as necessary to form an aqueous dispersion of toner particles. Thereafter, the toner is obtained by washing as necessary and drying, classification, and external additive treatment by various methods.

  The polymerizable monomer composition described above is prepared by mixing a dispersion in which a colorant is dispersed in the first polymerizable monomer with the second polymerizable monomer. preferable. That is, the colorant containing the pigment dispersion of the present invention is sufficiently dispersed by the first polymerizable monomer, and then mixed with the second polymerizable monomer together with the other toner materials, thereby obtaining The dye compound of the invention can be present in the toner particles in a better dispersed state.

  As a polymerization initiator, a well-known polymerization initiator can be mentioned, For example, an azo compound, an organic peroxide, an inorganic peroxide, an organometallic compound, a photoinitiator etc. are mentioned. Specifically, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvalero) Nitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), azo polymerization initiators such as dimethyl 2,2′-azobis (isobutyrate); benzoyl peroxide, ditert-butyl peroxide, tert- Organic peroxide polymerization initiators such as butyl peroxyisopropyl monocarbonate, tert-hexyl peroxybenzoate, and tert-butyl peroxybenzoate; inorganic peroxide polymerization initiators such as potassium persulfate and ammonium persulfate; Hydrogen oxide-ferrous, BPO-dimethylaniline, cerium (IV) salt-alcohol Redox initiators; and the like. Examples of the photopolymerization initiator include acetophenone series, benzoin ether series, and ketal series. These methods can be used alone or in combination of two or more.

  The addition amount of the polymerization initiator is preferably 0.1 to 20 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the polymerizable monomer. The kind of the polymerizable initiator is slightly different depending on the polymerization method, but is used alone or in combination with reference to the 10-hour half-life temperature.

  As the dispersion stabilizer, known inorganic and organic dispersion stabilizers can be used. Examples of inorganic dispersion stabilizers include calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, and calcium sulfate. , Barium sulfate, bentonite, silica, alumina and the like. Examples of the organic dispersion stabilizer include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, starch and the like. Nonionic, anionic and cationic surfactants can also be used. For example, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, calcium oleate and the like can be mentioned.

  Among the dispersion stabilizers, in the present invention, it is preferable to use a poorly water-soluble inorganic dispersion stabilizer that is soluble in acid. Further, when preparing a water-based dispersion medium using a hardly water-soluble inorganic dispersion stabilizer, these dispersion stabilizers are 0.2 to 2.0 parts by weight with respect to 100 parts by weight of the polymerizable monomer. It is preferable that the polymerizable monomer composition is used in a range from the viewpoint of droplet stability in an aqueous medium. Moreover, it is preferable to prepare an aqueous medium using water in the range of 300 to 3000 parts by weight with respect to 100 parts by weight of the polymerizable monomer composition.

  When preparing an aqueous medium in which a poorly water-soluble inorganic dispersion stabilizer is dispersed, in order to obtain dispersion stabilizer particles having a fine uniform particle size, the poorly water-soluble inorganic dispersion is stirred under high speed in water. It is preferred to prepare by forming a stabilizer. For example, when calcium phosphate is used as a dispersion stabilizer, a preferable dispersion stabilizer can be obtained by mixing a sodium phosphate aqueous solution and a calcium chloride aqueous solution under high speed stirring to form calcium phosphate fine particles.

  Even when the toner particles of the present invention are produced by suspension granulation, suitable toner particles can be obtained.

  Toner particles produced by the suspension granulation method are produced, for example, as follows. First, a colorant containing a pigment dispersion, a binder resin, wax and the like are mixed in a solvent to prepare a solvent composition. Next, the solvent composition is dispersed in an aqueous medium and particles of the solvent composition are granulated to obtain a suspension. Then, the toner particles can be obtained by heating the obtained suspension or removing the solvent by reducing the pressure.

  The solvent composition is preferably prepared by mixing a dispersion in which a colorant is dispersed in a first solvent with a second solvent. That is, the colorant containing the dye composition is sufficiently dispersed in the first solvent, and then mixed with the second solvent together with the other toner materials, so that the dye compound of the present invention is in a better dispersion state. It can be present in the toner particles.

  Examples of the solvent that can be used in the suspension granulation method include hydrocarbons such as toluene, xylene, and hexane; halogen-containing hydrocarbons such as methylene chloride, chloroform, dichloroethane, trichloroethane, and carbon tetrachloride; methanol, ethanol Alcohols such as butanol and isopropyl alcohol; polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol and triethylene glycol; cellosolves such as methyl cellosolve and ethyl cellosolve; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; Examples include ethers such as benzyl alcohol ethyl ether, benzyl alcohol isopropyl ether, and tetrahydrofuran; esters such as methyl acetate, ethyl acetate, and butyl acetate. These can be used alone or in admixture of two or more. Among these, in order to easily remove the solvent in the suspension, it is preferable to use a solvent having a low boiling point and capable of sufficiently dissolving the binder resin.

  As a usage-amount of a solvent, the range of 50-5000 mass parts is preferable with respect to 100 weight part of binder resin, and the range of 120-1000 weight part is more preferable.

  The aqueous medium used in the suspension granulation method preferably contains a dispersion stabilizer. As the dispersion stabilizer, known inorganic and organic dispersion stabilizers can be used. Examples of the inorganic dispersion stabilizer include calcium phosphate, calcium carbonate, aluminum hydroxide, calcium sulfate, and barium carbonate. Examples of organic dispersion stabilizers include polyvinyl alcohol, methylcellulose, hydroxyethylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, water-soluble polymers such as sodium polyacrylate and sodium polymethacrylate, sodium dodecylbenzenesulfonate, Anionic surfactants such as sodium octadecyl sulfate, sodium oleate, sodium laurate, potassium stearate, cationic surfactants such as laurylamine acetate, stearylamine acetate, lauryltrimethylammonium chloride, amphoteric such as lauryldimethylamine oxide Ionic surfactant, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene Surfactants such as nonionic surfactants down alkylamines, and the like.

  The amount of the dispersion stabilizer used is in the range of 0.01 to 20 parts by weight with respect to 100 parts by weight of the binder resin, from the viewpoint of droplet stability in the aqueous medium of the solvent composition. preferable.

  The adjustment method of the weight average particle diameter D4 and the number average particle diameter D1 of the toner differs depending on the toner particle manufacturing method. For example, in the case of the suspension polymerization method, it can be adjusted by controlling the concentration of the dispersing agent used at the time of preparing the aqueous dispersion medium, the reaction stirring speed, or the reaction stirring time.

  The pulverized toner can be produced using a production apparatus such as a mixer, a thermal kneader, or a classifier. First, a resin composition containing a binder resin and a colorant is sufficiently mixed by a mixer such as a Henschel mixer or a ball mill. Next, the resin composition is melted using a heat kneader such as a roll, a kneader, or an extruder. Further, the wax and the magnetic material are dispersed in the resin composition which is kneaded and kneaded to make the resin compositions compatible with each other. After cooling and solidification, toner particles can be obtained by pulverization and classification.

  Binder resins used in the pulverized toner include vinyl resins, polyester resins, epoxy resins, polyurethane resins, polyvinyl butyral resins, terpene resins, phenol resins, aliphatic or alicyclic hydrocarbons. Resin, aromatic petroleum resin, rosin, modified rosin and the like. Of these, vinyl resins and polyester resins are more preferable from the viewpoints of chargeability and fixability. In particular, when a polyester resin is used, the effect of charging property and fixing property is increased, which is preferable. These binder resins may be used alone or in combination of two or more. When using a mixture of two or more binder resins, it is preferable to mix resins having different molecular weights in order to control the viscoelastic properties of the toner.

  The glass transition temperature of the binder resin is preferably 45 to 80 ° C, more preferably 55 to 70 ° C. The binder resin preferably has a number average molecular weight (Mn) of 2,500 to 50,000 and a weight average molecular weight (Mw) of 10,000 to 1,000,000.

  When the binder resin is a polyester resin, the alcohol component / acid component is preferably in a mol% ratio of 45/55 to 55/45 in all components. The polyester resin becomes more environmentally dependent on the charging characteristics of the toner as the number of terminal groups of the molecular chain increases. Therefore, the acid value is preferably 90 mgKOH / g or less, and more preferably 50 mgKOH / g or less. The hydroxyl value is preferably 50 mgKOH / g or less, and more preferably 30 mgKOH / g or less. The glass transition temperature of the polyester resin is preferably 50 to 75 ° C, more preferably 55 to 65 ° C. The number average molecular weight (Mn) of the polyester resin is preferably 1,500 to 50,000, more preferably 2,000 to 20,000. The weight average molecular weight (Mw) of the polyester resin is preferably 6,000 to 100,000, more preferably 10,000 to 90,000.

  The method for producing toner particles by the emulsion aggregation method is obtained by mixing a dispersion liquid obtained by emulsifying a binder resin and a dispersion liquid of a colorant, and then aggregating and heating and fusing. Hereinafter, a detailed manufacturing method will be described.

  First, various dispersions (resin particle dispersion, colorant particle dispersion) are prepared. At this time, if necessary, a wax dispersion and other toner components may be mixed.

  The dispersion liquid is mixed and aggregated to form aggregate particles (aggregation process), and the aggregate particles are heated and fused (fusion process), washing process, and drying process to obtain toner particles.

  For each dispersion, a dispersant such as a surfactant can be used. Specifically, the colorant particle dispersion is obtained by dispersing a colorant together with a surfactant in an aqueous medium. As the colorant particles, for example, a media type dispersing machine such as a rotary shearing type homogenizer, a ball mill, a sand mill, or an attritor, a high pressure opposed collision type dispersing machine, or the like is preferably used.

  The resin particle dispersion and the wax dispersion can be obtained by dispersing the binder resin particles and the wax in an aqueous medium. The volume-based median diameter of the resin particles in the resin particle dispersion is preferably 0.005 to 1.0 μm, and more preferably 0.01 to 0.4 μm.

  The average particle diameter of the resin particles can be measured using, for example, a dynamic light scattering method (DLS), a laser scattering method, a centrifugal sedimentation method, a field-flow fractionation method, an electrical detector method, or the like. In addition, the average particle diameter in this invention is 50% of the volume reference | standard measured by the dynamic light-scattering method (DLS) / laser Doppler method at 20 degreeC and 0.01 mass% solid content concentration so that it may mention later. It means the cumulative particle size value (D50).

  Examples of the surfactant include water-soluble polymers, inorganic compounds, and ionic or nonionic surfactants. Preferably, ionicity having high dispersibility is preferable from the viewpoint of dispersibility, and an anionic surfactant is particularly preferably used. The molecular weight of the surfactant is preferably from 100 to 10,000, more preferably from 200 to 5,000.

  Specific examples of the surfactant include water-soluble polymers such as polyvinyl alcohol, methylcellulose, carboxymethylcellulose, and sodium polyacrylate; sodium dodecylbenzenesulfonate, sodium octadecylsulfate, sodium oleate, sodium laurate, stearic acid Anionic surfactants such as potassium; cationic surfactants such as laurylamine acetate and lauryltrimethylammonium chloride; zwitterionic surfactants such as lauryldimethylamine oxide; polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether , Surfactants such as nonionic surfactants such as polyoxyethylene alkylamine; tricalcium phosphate, aluminum hydroxide, calcium sulfate, calcium carbonate Um, and inorganic compounds such as barium carbonate. In addition, these may be used independently and may be used in combination of 2 or more types as necessary.

  The colorant particle dispersion can be prepared by dispersing a colorant in an aqueous medium together with a surfactant. First, each compound represented by any one of formulas (1) to (3) is prepared as a dispersion. It is also possible to prepare a dispersion liquid in which the compounds represented by the formulas (1) to (3) are mixed. As the colorant particles, for example, a media type dispersing machine such as a rotary shearing type homogenizer, a ball mill, a sand mill, or an attritor, a high pressure opposed collision type dispersing machine, or the like is preferably used.

  The usage-amount of surfactant is 0.01-10 mass parts with respect to 100 mass parts of coloring agents, Preferably, it is 0.1-5 mass parts. In particular, since it is easy to remove the surfactant in the toner particles, it is preferably used at 0.5 to 3 parts by mass.

  The method for forming the aggregate particles is not particularly limited, but a pH adjuster, a flocculant, a stabilizer, etc. are added and mixed in the above mixed solution, and the temperature, mechanical power (stirring), etc. are adjusted. The method of adding suitably can be illustrated suitably.

  Examples of the pH adjuster include alkalis such as ammonia and sodium hydroxide, and acids such as nitric acid and citric acid.

  Examples of the flocculant include divalent or higher-valent metal complexes in addition to inorganic metal salts such as sodium chloride, magnesium carbonate, magnesium chloride, magnesium nitrate, magnesium sulfate, calcium chloride, and aluminum sulfate.

  Examples of the stabilizer of the present invention include the surfactants described above.

  The average particle size of the aggregate particles formed here is usually controlled to be approximately the same as the average particle size of the toner particles to be obtained. Control can be easily performed, for example, by appropriately setting / changing the temperature at the time of addition / mixing of the flocculant or the like and the conditions of the stirring and mixing. Furthermore, in order to prevent fusion between the toner particles, the pH adjusting agent, the surfactant and the like can be appropriately added.

  In the fusing step, toner particles are formed by fusing the aggregate particles with heating. The heating temperature may be between the glass transition temperature (Tg) of the resin contained in the aggregate particles and the decomposition temperature of the resin. For example, under the same agitation as in the aggregation step, the progress of aggregation is stopped by adding a surfactant or adjusting the pH, and the aggregate particles are fused by heating to a temperature equal to or higher than the glass transition temperature of the resin particles.・ Match them together. The heating time may be such that the fusion is sufficiently performed, specifically, it may be performed for about 10 minutes to 10 hours. In addition, before and after the fusion step, it may further include a step (attachment step) in which a fine particle dispersion in which fine particles are dispersed is added and mixed to attach the fine particles to the aggregate particles to form a core / shell structure. is there.

  The toner particles obtained after the fusing step are washed, filtered, dried and the like under appropriate conditions to obtain toner particles. In this case, in order to ensure sufficient charging characteristics and reliability as a toner, it is preferable to sufficiently wash the toner particles. As a washing method, for example, a suspension containing toner particles is filtered, and the obtained filtrate is stirred and washed with distilled water and further filtered. From the viewpoint of the chargeability of the toner, it is preferable to repeat the washing until the electric conductivity of the filtrate is 150 μS / cm or less.

  Furthermore, as described above, an external additive such as an inorganic fine powder may be added to the surface of the obtained toner particles.

  For the drying, a known method such as a normal vibration type fluid drying method, a spray drying method, a freeze drying method, or a flash jet method can be used. The moisture content of the toner particles after drying is preferably 1.5% by mass or less, and more preferably 1.0% by mass or less.

  The toner of the present invention may be either magnetic toner or non-magnetic toner. When used as a magnetic toner, the toner particles constituting the toner of the present invention may be used by mixing magnetic materials. Examples of such magnetic materials include iron oxides such as magnetite, maghemite, and ferrite, iron oxides including other metal oxides, metals such as Fe, Co, and Ni, or these metals and Al, Co, Examples thereof include alloys with metals such as Cu, Pb, Mg, Ni, Sn, Zn, Sb, Be, Bi, Cd, Ca, Mn, Se, Ti, W, and V, and mixtures thereof.

  Hereinafter, a method for producing a liquid developer will be described. First, in order to obtain a liquid developer, it is produced by dispersing or dissolving a colored resin powder and, if necessary, an auxiliary agent such as a charge control agent and wax in an electrically insulating carrier liquid. Alternatively, it may be prepared by a two-stage method in which a concentrated toner is first prepared and further diluted with an electrically insulating carrier solution to prepare a developer.

  The colored resin powder can also be used by adding a known colorant such as a pigment or dye alone or in combination of two or more. The wax and colorant are the same as described above.

  The charge control agent is not particularly limited as long as it is used in a liquid developer for electrostatic charge development. For example, cobalt naphthenate, copper naphthenate, copper oleate, cobalt oleate, Zirconium octylate, cobalt octylate, sodium dodecylbenzenesulfonate, calcium dodecylbenzene sulfonate, soybean lecithin, aluminum octoate and the like.

The electrically insulating carrier liquid is not particularly limited, but it is preferable to use an organic solvent having a high electric resistance of 10 ⁹ Ω · cm or more and a low dielectric constant of 3 or less, for example. Specific examples include aliphatic hydrocarbon solvents such as hexane, pentane, octane, nonane, decane, undecane, and dodecane, Isopar H, G, K, L, M (manufactured by Exxon Chemical Co., Ltd.), linearlen dimer The thing of the temperature range whose boiling point is 68-250 degreeC, such as A-20 and A-20H (made by Idemitsu Kosan Co., Ltd.), is preferable. These may be used alone or in combination of two or more.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further in detail, this invention is not limited to these Examples. In the text, “parts” and “%” are based on mass unless otherwise specified. The obtained reaction product was identified by an analysis method using MALDI MS (autoflex apparatus, manufactured by Bruker Daltonics). In MALDI MS, the detection ion adopted a negative mode.

  <Synthesis Example 1: Production of Compound (2-39)>

  A methanol (MeOH) 20 mL solution of 0.721 g of the amine compound was cooled to 5 ° C., and 2 mL of concentrated sulfuric acid and 1.4 mL of nitrosylsulfuric acid (40%) were added dropwise (diazotized A solution). Separately, a solution of 0.496 g of the pyridone compound in 20 mL of methanol (MeOH) is cooled to 5 ° C., and the diazotized solution A is slowly added dropwise to the solution so that the temperature is kept at 5 ° C. or lower. For 20 minutes. After completion of the reaction, an aqueous sodium carbonate solution was added dropwise to neutralize the pH to 6, followed by extraction with chloroform. Then, the solid obtained by distilling off the solvent was purified by column chromatography (developing solvent: heptane / ethyl acetate), and recrystallized with a heptane solution to obtain 0.8 g of compound (2-39). .

[Results of analysis for compound (2-39)]
Mass spectrometry by MALDI MS: m / z = 618.612 (M−H) ⁻

<Synthesis Examples 2-34>
In accordance with Synthesis Example 1, the compounds (1-5), (1-15), (1-26), (1-30), (1-34), (1-38), (1-39), (1-41), (1-47), (1-50), (2-3), (2-8), (2-17), (2-26), (2-27), (2 -30), (2-38), (2-40), (2-42), (2-49), (2-50), (2-51), (2-52), (2-53) ), (3-5), (3-19), (3-42), (3-43), (3-44), (3-45), (3-46), (3-52), (3-54) was synthesized and identified by mass spectrometry by MALDI MS.

  The yellow toner of the present invention and the comparative yellow toner were produced by the method described below.

<Example 1>
A mixture of 5 parts of exemplary compound (1-26) and 120 parts of styrene was dissolved by an attritor (Mitsui Mining Co., Ltd.) to obtain a pigment dispersion (1-26).

  High-speed stirrer K. In a 2 L four-necked flask equipped with a homomixer (Primics Co., Ltd.), 710 parts of ion-exchanged water and 450 parts of a 0.1 mol / l-trisodium phosphate aqueous solution were added to adjust the rotational speed to 12000 rpm, and 60 Warmed to ° C. To this, 68 parts of a 1.0 mol / l-calcium chloride aqueous solution was gradually added to prepare an aqueous dispersion medium containing a minute poorly water-soluble dispersion stabilizer calcium phosphate.

The following materials were mixed and heated to 60 ° C. K. It was uniformly dissolved and dispersed at 5000 rpm using a homomixer.
-Dye dispersion (1-26) 133.2 parts-Styrene monomer 46.0 parts-n-Butyl acrylate monomer 34.0 parts-Aluminum salicylate compound 2.0 parts (Orient Chemical Industries, Ltd. Bontron) E-88)
-Polar resin 10.0 parts (polycondensation product of propylene oxide modified bisphenol A and isophthalic acid, Tg = 65 ° C., Mw = 10000, Mn = 6000)
Ester wax 25.0 parts (peak temperature of maximum endothermic peak in DSC measurement = 70 ° C., Mn = 704)
・ Divinylbenzene monomer 0.10 parts

  In this, 10 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was dissolved to prepare a polymerizable monomer composition. The polymerizable monomer composition was put into an aqueous medium and granulated for 15 minutes while maintaining the rotation speed of 12000 rpm. Thereafter, the stirrer was changed from a high-speed stirrer to a propeller stirring blade, and the polymerization was continued for 5 hours at a liquid temperature of 60 ° C., then the liquid temperature was raised to 80 ° C., and the polymerization was further continued for 3 hours. After completion of the polymerization reaction, the remaining monomer was distilled off at 80 ° C./reduced pressure, and then the liquid temperature was cooled to 30 ° C. to obtain a polymer fine particle dispersion.

  Next, the polymer fine particle dispersion was transferred to a washing container, and while stirring, dilute hydrochloric acid was added to adjust the pH to 1.5, followed by stirring for 1 hour. Solid-liquid separation was performed with a filter to obtain polymer fine particles. Redispersion of polymer fine particles in water and solid-liquid separation were repeated until the compound of phosphoric acid and calcium containing calcium phosphate was sufficiently removed. Thereafter, the polymer fine particles finally solid-liquid separated were sufficiently dried with a dryer to obtain yellow toner base particles (toner particles before addition of external additives).

For 100 parts of the yellow toner base particles obtained,
1.00 parts of hydrophobic silica fine powder (number average primary particle diameter 7 nm) surface-treated with hexamethyldisilazane,
Rutile type titanium oxide fine powder (number average primary particle diameter 45 nm) 0.15 part, rutile type titanium oxide fine powder (number average primary particle diameter 200 nm) 0.50 part with Henschel mixer (manufactured by Nippon Coke Industries Co., Ltd.) The yellow toner (1) of the present invention was obtained by dry mixing for a minute.

<Examples 2-32>
In Example 1, yellow toners (2) to (32) of the present invention were obtained in the same manner as in Example 1 except that the exemplified compound (1-26) was changed to the exemplified compounds shown in Tables 8 and 9.
<Comparative Examples 1-4>
In Example 1, except that the compound (1-26) was changed to the comparative compounds (C-1) to (C-4), in the same manner as in Example 1, the comparative yellow toner (ratio 1) to (ratio) 4) was obtained. Comparative compounds (1) to (4) are shown below.

<Example 33>
82.6 parts of styrene, 9.2 parts of n-butyl acrylate, 1.3 parts of acrylic acid, 0.4 part of hexanediol acrylate, and 3.2 parts of n-lauryl mercaptan were mixed and dissolved. To this solution, an aqueous solution of 150 parts of ion-exchanged water of 1.5 parts of Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd.) was added and dispersed. Further, while stirring slowly for 10 minutes, an aqueous solution of 10 parts of ion-exchanged water of 0.15 parts of potassium persulfate was added. After nitrogen substitution, emulsion polymerization was performed at 70 ° C. for 6 hours. After completion of the polymerization, the reaction solution was cooled to room temperature, and ion exchange water was added to obtain a resin particle dispersion having a solid content concentration of 12.5% by mass and a volume-based median diameter of 0.2 μm.

  100 parts of ester wax (peak temperature of maximum endothermic peak in DSC measurement = 70 ° C., Mn = 704) and 15 parts of neogen RK are mixed with 385 parts of ion-exchanged water, and a wet jet mill JN100 (manufactured by Toko) is used. It was dispersed for about 1 hour to obtain a wax dispersion. The concentration of the wax particles in the wax dispersion was 20% by mass.

  Compound (3-52) is dispersed by mixing 100 parts of Exemplified Compound (3-52) and 15 parts of Neogen RK with 885 parts of ion-exchanged water and dispersing for about 1 hour using a wet jet mill JN100 (manufactured by Toko). A liquid was obtained. The volume-based median diameter of the colorant particles in the compound (3-52) dispersion was 0.2 μm, and the concentration of the compound (3-52) dispersion was 10% by mass.

  After dispersing 160 parts of the resin particle dispersion, 10 parts of the wax dispersion, 10 parts of the compound (3-52) dispersion and 0.2 part of magnesium sulfate using a homogenizer (manufactured by IKA: Ultra Turrax T50), While stirring, the mixture was warmed to 65 ° C. After stirring at 65 ° C. for 1 hour, observation with an optical microscope confirmed that aggregate particles having an average particle diameter of about 6.0 μm were formed. After adding 2.2 parts of Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd.), the temperature was raised to 80 ° C. and stirred for 120 minutes to obtain fused toner particles. After cooling, it was filtered and the filtered solid was stirred and washed with 720 parts of ion exchange water for 60 minutes. The solution containing the toner particles was filtered, and the same washing was repeated until the electric conductivity of the filtrate became 150 μS / cm or less. The toner base particles were obtained by drying using a vacuum dryer.

To 100 parts of the toner base particles, 1.8 parts of hydrophobized silica fine powder having a specific surface area measured by the BET method of 200 m ² / g was dry-mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). Toner (33) was obtained.

<Example 34>
Binder resin (polyester resin) 100 parts (Tg 55 ° C., acid value 20 mgKOH / g, hydroxyl value 16 mgKOH / g, molecular weight: Mp4 500, Mn2300, Mw38000), Exemplified compound (3-54) 5 parts, 1,4-di After thoroughly mixing 0.5 parts of an aluminum compound of t-butylsalicylate and 5 parts of paraffin wax (maximum endothermic peak temperature 78 ° C.) with a Henschel mixer (FM-75J type, manufactured by Mitsui Mining Co., Ltd.), a temperature of 130 ° C. Was kneaded at a feed amount of 60 kg / hr (PCM-45 type, manufactured by Ikekai Steel Co., Ltd.) (kneaded material temperature at the time of discharge was about 150 ° C.). The obtained kneaded product was cooled and coarsely crushed with a hammer mill, and then finely pulverized with a mechanical pulverizer (T-250: manufactured by Turbo Kogyo Co., Ltd.) at a Feed amount of 20 kg / hr. Further, the obtained toner finely pulverized product was classified by a multi-division classifier using the Coanda effect to obtain toner base particles.

To 100 parts of the toner base particles, 1.8 parts of hydrophobized silica fine powder having a specific surface area measured by the BET method of 200 m ² / g was dry-mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). Toner (34) was obtained.

<Example 35>
In Example 1, 5 parts of Exemplary Compound (1-26) was added to C.I. I. Pigment Yellow 155 (manufactured by Clariant, trade name “Toner Yellow 3GP”) 2.5 parts, 2.5 parts of Exemplified Compound (2-39) was changed, and the mixture was dispersed with a paint shaker and dye dispersed A yellow toner (35) was obtained in the same manner as in Example 1 except that it was used as the body (2-39 + PY-155).

(1) Evaluation of blocking property 1 g of the above yellow toner was placed in a transparent sample bottle, left uncovered for 3 days at room temperature of 50 ° C. and humidity of 60%, and visually confirmed.

The evaluation was performed as follows, and it was judged that the toner had good blocking properties if it did not aggregate and could not be agglomerated.
A: The lump is not visible, and the blockiness is good.
B: Mass can be seen (low blocking property)

(2) Evaluation of environmental stability of charging The yellow toner was measured for changes in weight under conditions of a temperature of 40 ° C., a humidity of 95%, and 3 hours with a vapor adsorption / desorption measuring device (Q5000SA, TA Instruments).

The evaluation was performed as follows. When the moisture absorption ratio (weight change ratio) was 2.5% or less, it was judged that there was no leakage at a temperature of 40 ° C. and a humidity of 95%, and the charging characteristics were good.
A: 2.5% or less (good charging characteristics)
B: Greater than 2.5% (charging property is not sufficient)

  Storage stability A when blocking and charging environmental stability are both A, storage stability B when blocking and charging environmental stability are either B, blocking stability and charging environmental stability A sample having both B was designated as storage stability C. Each evaluation is shown in Table 8.

  From Table 8, the comparative compound group in which the carbon number of the alkyl group is not within the range of the present invention is not sufficiently stable in storage, but the compound group in which the carbon number of the alkyl group is within the range of the present invention is stored. It turns out that it is excellent in stability.

(3) Image sample evaluation using yellow toner Next, an image sample was output using the toner described above, and image characteristics described later were compared and evaluated. For comparison of image characteristics, paper passing durability was performed using a modified machine of LBP-5300 (manufactured by Canon) as an image forming apparatus (hereinafter abbreviated as LBP). As a modification, the developing blade in the process cartridge (hereinafter referred to as CRG) was replaced with a SUS blade having a thickness of 8 μm. Then, a blade bias of −200 V can be applied to the developing bias applied to the developing roller which is a toner carrier. For the evaluation, a CRG individually filled with each yellow toner was prepared for each evaluation item. Each CRG filled with each yellow toner was set to LBP and evaluated for each evaluation item described below.

First, for each image sample of the toner described above, the chromaticity (L ^* , a ^* , b ^* ) in the L ^* a ^* b ^* color system was measured with a reflection densitometer SpectroLino (manufactured by Gretag Macbeth).

<Light resistance evaluation of toner>
The image sample obtained at the time of chromaticity measurement was put into a xenon test apparatus (AtlasCi4000, manufactured by Suga Test Instruments Co., Ltd.) (illuminance: 0.39 W / m ^{2 at} 340 nm, temperature: 40 ° C., relative humidity: (60%) for 40 hours. The reflection density of the printed matter was measured before and after the exposure test. When the initial chromaticity is a ₀ ^* , b ₀ ^* , and L ₀ ^*, and the chromaticity after exposure is a ^* , b ^* , and L ^* , respectively, the color difference ΔE is defined and calculated as follows: . The obtained results are shown in Table 2. In Table 9, PY-155 is C.I. I. Pigment Yellow 155 is shown.

The evaluation criteria are as follows.
A: ΔE <5.00 (light resistance is very excellent)
B: 5.00 ≦ ΔE <10.00 (excellent light resistance)

Claims (11)

A yellow toner having toner particles containing a binder resin and a colorant,
The colorant contains at least one compound selected from the group consisting of a compound represented by the following formula (1), a compound represented by the following formula (2), and a compound represented by the following formula (3). Yellow toner characterized by.

(In the formulas (1) to (3),
R ¹ , R ¹¹ , R ¹² and R ²¹ each independently represents an alkyl group having 3 or more carbon atoms.
R ³ , R ¹³ and R ²³ each independently represents an alkyl group.
R ⁴ , R ¹⁴ , and R ²⁴ each independently represent a linear alkyl group having 3 or more carbon atoms. ) 2. The yellow toner according to claim ¹ , wherein R ¹ , R ¹¹ , R ¹² and R ²¹ are alkyl groups having 3 to 8 carbon atoms. The yellow toner according to claim 1, wherein R ⁴ , R ¹⁴ , and R ²⁴ are each independently a linear alkyl group having 3 to 8 carbon atoms. In said Formula (1)-(3), R < ¹ >, R <^11> , R < ¹² > and R < ²¹ > are respectively independently n-octyl group or 2-ethylhexyl group. The yellow toner described. 5. The yellow toner according to claim 1, wherein in the formulas (1) to (3), R ³ , R ^13, and R ²³ are alkyl groups having 1 to 8 carbon atoms. The compound represented by the formula (1), the compound represented by the formula (2), or the compound represented by the formula (3) is represented by the following formulas (1-26), (1-30), (1-38). ), (1-39), (1-41), (1-47), (1-50), (2-26), (2-27), (2-30), (2-38), (2-39), (2-40), (2-42), (2-49), (2-50), (2-51), (2-52), (2-53), (3 -42), (3-43), (3-44), (3-45), (3-46), (3-52), (3-54) The yellow toner according to any one of 1 to 5.


The yellow toner according to any one of claims 1 to 6, wherein the toner particles are the following (i) or (ii) toner particles:
(I) A dispersion obtained by dispersing a polymerizable monomer composition containing the colorant and a polymerizable monomer in an aqueous medium to prepare a suspension, and polymerizing the polymerizable monomer. Toner particles containing a resin,
(Ii) Toner particles obtained by suspending a solution containing the colorant and the binder resin in an aqueous solvent and granulating the solution.   7. The toner particle according to claim 1, wherein the toner particles are toner particles obtained by mixing a dispersion liquid obtained by emulsifying and dispersing the binder resin and a dispersion liquid of the colorant, and aggregating and heat-fusion. The yellow toner according to item.   The yellow toner according to claim 1, wherein the toner particles are toner particles obtained by kneading and pulverizing a resin composition containing the binder resin and the colorant.   The colorant further comprises C.I. I. The yellow toner according to claim 1, comprising Pigment Yellow 180, 155, 150, or 74.   The yellow toner according to claim 1, wherein the toner particles further contain a wax.